JPH0753780B2 - Polymer containing pendant peroxide group and process for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field The present invention provides a novel pendant peroxide group-containing polymer and a process for producing the same.

(Prior art and its problems) Compounds having both a polymerizable double bond and a peroxide group in one molecule, such as allyl peroxycarbonate, are known. However, since the double bond of this compound is an allyl group, its homopolymerizability and copolymerizability are not sufficient. In addition, a method of obtaining a polymer having no peroxide group by an ordinary radical reaction and introducing a peroxide group into this polymer cannot be carried out under mild conditions, the decomposition of the peroxide group occurs, and the conventional technique cannot achieve this. Probably not.

It is known that peroxycarbamic acid is synthesized by the reaction of isocyanate with peroxide (see below).

[Wherein R _p and R _q are compounds in which an alkyl group, an aryl group and other organic atomic groups are substituted. However, a compound having an unsaturated double bond as R _p has not yet been reported.

The present invention has the formula: [In the formula, R ¹ is hydrogen or a lower alkyl group, and R is 2 carbon atoms.
An alkyl group or a ketoalkyl group which may have an aromatic ring and has A to A, A is a direct bond, Indicates. ] And the formula: [Wherein P, Q, Y and Z are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aralkyl group having 10 or less carbon atoms, a halogen, a cyano group, -O -COR '(R' is an alkyl group having 1 to 6 carbon atoms,
An aryl group having 8 or less carbon atoms, an alkylaryl group, a haloaryl group, an alkoxyaryl group, a haloalkyl group having 4 or less carbon atoms, or a hydroxyalkyl group is shown. ), Cyanomethyl group, amide group, —CH ₂ OCOR ″
(R ″ is an alkyl group having 9 or less carbon atoms, a haloalkyl group,
Or a phenyl group is shown. ), COORa (Ra is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group, and 10 carbon atoms
The following aryl groups or aralkyl groups having 10 or less carbon atoms,
A sulfoalkyl having 2 to 6 carbon atoms or an acid phosphoroxyalkyl having 2 to 3 carbon atoms is shown. ] A repeating unit represented by the formula: wherein the repeating unit of the formula (I) is m (where m is a positive integer) and the repeating unit of the formula (II) is n (n is 0 or positive). The present invention provides a polymer having a molecular weight of 1,000 to 100,000 and a process for producing the same.

The polymer of the present invention is basically synthesized by the following two methods. Of course, it is not limited to these two methods.

Manufacturing Method 1 The first manufacturing method of the present invention is a formula [Wherein R ¹ , R and A have the same meanings as described above. ] It is obtained by homopolymerization of a peroxide monomer represented by or copolymerization with another monomer.

The method for producing the peroxide monomer (III) will be described.

The starting materials for the peroxide monomer include the following three kinds.

[In the formula, R ¹ represents hydrogen or a lower alkyl group (eg, methyl, ethyl, propyl group, etc.). ] The above-mentioned starting material (isocyanate compound) (VI) is Angew.
Chem, Int. Ed. Engl, 18 (1979) No. 4 and the like. Isocyanate compound (VII) is disclosed in JP-A-60-115.
Method of 557 Publication and D. Macromoreclere
Chemie (Die Makromoleklare Chemie) 131 (1970) 247
~ 257 (No. 3199) intermediates and various other methods. The isocyanate compound (VIII) can be obtained, for example, by the method described in British Patent 1,252,099.

The hydroperoxide that reacts with the above isocyanate compound has the formula: HO-O-R [wherein R has the same meaning as described above. ] A hydrogen atom of hydrogen peroxide is substituted with an alkyl group or other organic atomic group, and a —OOH group is present in the molecule.
Specific examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, peracetic acid and 2,5-dimethyl-2,5-dihydroperoxide. Oxyhexane, 2,5-dimethyl-2,5-dihydroperoxyhexane-3 and the like can be mentioned.

Hydroperoxides are available in the form of concentrates or diluents. When it is available in the form of an aqueous solution, water may be replaced with an organic solvent by an extraction method. Further, although it can be used in the reaction as an aqueous solution, a by-product (amide) is produced,
Not preferable.

The reaction may be carried out in an inert solvent if necessary.

The inert solvent is not particularly limited as long as it does not adversely affect the reaction, and various solvents can be used. For example, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, hydrocarbon ethers such as petroleum ether and petroleum benzine. Solvent, carbon tetrachloride, chloroform, 1,2
-Halogenated hydrocarbon solvents such as dichloroethane, ether solvents such as ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran,
It may be appropriately selected from ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and isophorone, esters such as ethyl acetate and butyl acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide and the like. These may be used alone or as a mixture.

The reaction is carried out at a temperature at which hydroperoxide does not decompose, especially -20
It is preferable to carry out at -10 ° C.

If the temperature is higher than 10 ° C, hydroperoxides may be decomposed, while if the temperature is too low, the reaction rate becomes small, which is disadvantageous. In the reaction, the use of a catalyst may be considered, but usually the need for a catalyst is not recognized. A polymerization inhibitor may be added to the reaction.

The peroxide monomer (III) may be polymerized alone,
It may be copolymerized with other assembling monomers. The polymerizable monomer basically has the formula: [Wherein P, Q, Y and Z have the same meanings as described above. ] For convenience, it is classified into an active hydrogen-containing ethylenically unsaturated compound and an ethylenically unsaturated compound having no active hydrogen. Examples of active hydrogen-containing ethylenically unsaturated compounds include unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, 2-isopropylacrylic acid, tran.
s (cis) -2-decenoic acid, α-chloroacrylic acid, β-Tr
ans-nitroacrylic acid and the like; unsaturated alcohols such as the above-mentioned unsaturated acid and glycolic acid (ethylene glycol,
Propylene glycol, etc.), croton alcohol, cinnamyl alcohol, o-hydroxystyrene, etc .; unsaturated amides such as amides of the above unsaturated acids, typically acrylic acid amides, methacrylic acid amides, crotonic acid amides. , Cinnamic acid amide, p-benzamide styrene, etc .; unsaturated sulfonic acids or salts thereof, for example, 2-sulfoethyl acrylate, methacrylic acid-2-
Sulfoethyl, 4-sulfophenyl acrylate; unsaturated phosphoric acid such as acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate and the like; and unsaturated amine such as allylamine, o-aminostyrene, m-aminostyrene, methacrylic acid t. −
Examples include butylaminoethyl, 7-amino-3,7-dimethyloctyl acrylate and the like. These may be used alone or as a mixture.

Examples of ethylenically unsaturated monomers having no active hydrogen are: monoolefin and diolefin hydrocarbons,
That is, a monomer having only hydrogen atoms and carbon atoms, for example, styrene, α-methylstyrene, ethylene, propylene, butylene, amylene, hexylene, butadiene-
1,3, isoprene and the like; halogenated monoolefins and diolefin hydrocarbons, ie monomers having carbon atoms, hydrogen atoms and one or more halogen atoms, eg
α-chlorostyrene, 2,5-dibromostyrene, 3,4-dichlorostyrene, ortho, meta and para-fluorostyrene, 2,6-dichlorostyrene, 3-fluoro-4-
Chlorostyrene, 3-chloro-4-fluorostyrene,
2,4,5-Trichlorostyrene, 2-chlorohexene, 2
-Bromoheptene, 2-iodopentene, cis and trans-1,2-dichloroethylene, 1,2-dibromoethylene, 1,2-difluoroethylene, 1,2-diiodoethylene, chloroethylene (vinyl chloride), 1,1 -Dichloroethylene (vinylidene chloride), 1,1-dibromoethylene, 1,1,2-trifluoroethylene, chlorobutadiene and other halogenated diolefin compounds;
Esters of organic and inorganic acids such as vinyl acetate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl benzoate, vinyl halobenzoate, vinyl-p-methoxybenzoate, methyl (meth) acrylate, ethyl (meth). Acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, methyl crotonate and ethyl tiglate, isopropenyl acetate, isopropenyl butyrate, isopropenyl valerate, isopropenyl capro Ate, isopropenyl benzoate, isopropenyl-p-chlorobenzoate, vinyl-α-chloroacetate, vinyl-α-bromovalerate; esters derived from alkenyl alcohol, such as allyl chloride, allyl cyanide, allyl chloride carbonate, Allyl nitrate, allyl thiocyanate, allyl formate, allyl acetate, acetate propionate, allyl butyrate, allyl crotonate, allyl aminoacete , Allyl racetoacetate, allyl thioacetate, β-ethylallyl alcohol, β-propylallyl alcohol; organic nitriles,
For example, acrylonitrile, methacrylonitrile, ethacrylonitrile, 3-octenenitrile, crotonitrile, oleonitrile and the like can be mentioned.

The polymerization is carried out by radical copolymerization of the above monomers in a solvent inert to the polymerization. A usual radical initiator is preferably used as the polymerization initiator. For example, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, tetramethylthiuram disulfide, 2,2'-
Azobis (4-methoxy-2,4-dimethylvaleronitrile), acetylcyclohexylsulfonyl peroxide, 2,2'-azobis (2,4-dimethylvaleronitrile)
Etc. The amount of the initiator compounded is usually 0.1 to 10% by weight based on the amount of the monomer. Polymerization temperature is usually 40 ~ 150 ℃,
It is preferably 40 to 80 ° C. As the solvent inert to the polymerization, the above-mentioned inert solvent, various alcohols, or a mixture thereof is used.

Production Method 2 The second synthetic method of the polymer of the present invention is to subject the isocyanate compound (VI), (VII) or (VIII) to homopolymerization or copolymerization in advance, and then to obtain an isocyanate group and a hydrol It is obtained by reacting with a peroxide (HO-OR [R has the same meaning as above]). As the isocyanate compound, hydroperoxide and the like that can be used, those described in the above Production Method 1 can be used. However, since the isocyanate compound is used in an unreacted state, it is necessary to avoid the use of a compound that reacts with the isocyanate group to inhibit the formation of the target product. Therefore, a solvent containing active hydrogen cannot be used in the reaction. Also, a monomer having no active hydrogen is used in the copolymerization. Other reaction conditions are almost the same as those in the production method 1.

The reaction between the polymer and hydroperoxide may be carried out by an equimolar reaction, and all the isocyanate groups may be subjected to the reaction with hydroperoxide, but the reaction with hydroperoxide may be carried out with some isocyanate groups, and other The isocyanate group of may be left as an active site for other reaction. Also,
The isocyanate groups may be reacted with other active hydrogen containing compounds to introduce other functional groups into the polymer. For example, alcohols, phenolic compounds, active methylene compounds, lactams, N-hydroxyimides, oximes, imidazoles, triazoles and amines often used as isocyanate group blocking agents can be reacted. In addition, other fluorine-containing compounds,
By reacting a melamine derivative, a spiro compound, a Si group-containing compound, glycidols, a photocrosslinkable compound, a UV absorber, etc., they can be made to coexist with a peroxide group. Alternatively, a polymerizable double bond may be introduced into the polymer by reacting with an active hydrogen-containing ethylenically unsaturated compound.

(Action and Effect) The polymer of the present invention has the following structure schematically.

The portion a is dissociated into —A—NH—COO · and BO · by heating and is used for radical polymerization. This group is further decarboxylated-
Change to A-NH. This dissociated product is also subjected to radical polymerization. Therefore, the polymer of the present invention has a radical initiation ability,
Moreover, a graft polymer can be formed from this radical moiety. Various functional groups are introduced into the pendant group represented by P. For example, when an ethylenically unsaturated group is introduced into P, a one-part curable resin composition is obtained with the peroxide moiety of (a).

The feature of the production method of No. 1 is that the selection of solvent or other copolymerizable monomer is wide because the isocyanate group is already blocked. Further, upon polymerization, the copolymer can be synthesized without gelation due to the influence of water in the system.

In the production method 2, ordinary radical polymerization can be selected without considering the decomposition temperature of the peroxide group, and there is no decomposition loss of hydroperoxide due to heat. In introducing a peroxide group, since a highly reactive isocyanate is used, mild conditions can be used, and a thermally unstable peroxide can be used.

(Examples) The present invention will be described in more detail with reference to Examples.

Example 1 Synthesis of Copolymer Having Pendant Acyl Isocyanate Blocked with t-Butyl Hydroperoxide 2.2 g (20 mmol) of methacryloyl isocyanate and 2.0 g of butyl acetate were cooled to a temperature of 15 to 20 ° C. to obtain t-butyl. 6.0 g (20 mmol) of a 20% toluene solution of hydroperoxide was added dropwise over 5 minutes. As a toluene solution of t-butyl hydroperoxide, an 80% t-butyl hydroperoxide aqueous solution was extracted several times with toluene and then dried with Mg ₂ SO ₄ , and the content was determined by NMR and used. After confirming disappearance of νNCO and absorption of the adduct at ν = 1800 cm ¹ by IR spectrum, 4.4 g of n-butyl acrylate and 2.0 g of methyl methacrylate
Was added and the mixture was heated with stirring at 80 ° C. Then as an initiator 2,
2'-azobis (2,4-dimethyl) valeronitrile (V-
65) (3%, 300 mg) was dissolved in 5 g of butyl acetate and added dropwise in about 30 minutes. Then, by aging for 1 hour, a target copolymer was obtained with a polymerization rate of 61% and ▲ ▼ = 1590.

Example 2 Copolymer having pendant acylisocyanate blocked with t-butyl hydroperoxide 1.7 g (15 mmol) of methacryloyl isocyanate, 4.0 g of n-butyl acrylate, 2.0 g of styrene, and 2,2'- as an initiator. 231 mg (3%) of azobis (2,4-dimethyl) valeronitrile (V-65) was mixed and added dropwise to 10.0 g of butyl acetate heated to 110 ° C. over 1 hour. After aging at this temperature for 2 hours, the mixture was cooled to 0 to 5 ° C., and a mixture of 2.7 g of 50% benzene solution of t-butyl hydroperoxide and 4.2 g of butyl acetate was added dropwise over 10 minutes and stirred. Continued. A benzene solution of t-butyl hydroperoxide is
The aqueous solution of t-butyl hydroperoxide was extracted several times with benzene and dried with Mg ₂ SO ₄ , and the content was determined by NMR and used. Confirm the absorption of νNCO in the IR spectrum,
The target resin was obtained with a polymerization rate of 80% and ▲ ▼ = 6300.

Example 3 Copolymer Having Pendant Acyl Isocyanate Blocked with Cumene Hydroperoxide 2.8 g (25 mmol) of methacryloyl isocyanate, 8.0 g of n-butyl acrylate, 4.0 g of styrene and 2,2'-azobis (2 as an initiator 444 mg (3%) of 4,4-dimethyl) valeronitrile (V-65) was mixed and added dropwise to 15.0 g of butyl acetate heated to 110 ° C. After aging for 2 hours at this temperature, the mixture was cooled to -5 ° C. Then, a mixture of 5.2 g (25 mmol) of cumene hydroperoxide (73% solution) and 1.0 g of butyl acetate was added dropwise in about 5 minutes. After completion of dropping, the mixture was stirred for 1 hour, the disappearance of absorption of νNCO was confirmed by IR spectrum, and a target resin was obtained at a polymerization rate of 80% and ▲ ▼ = 7200.

Example 4 Copolymer having pendant isocyanate blocked with t-butyl hydroperoxide 1.6 g (10 mmol) of isocyanate ethyl methacrylate,
Butyl acrylate 4.0 g, styrene 1.5 g, and 2,2′-azobis (2,4-dimethyl) valeronitrile (V-65) 220 mg (3%) as an initiator were mixed and heated to 100 ° C. butyl acetate 11.3 g It was dripped into it in 1 hour. Then, after aging for 1 hour, the mixture was cooled to 0 ° C., 1.8 g (10.0 mmol) of a 50% benzene 50% solution of t-butyl hydroperoxide was dissolved in 4.5 g of butyl acetate, and added dropwise in about 30 minutes. Thereafter, 20 mg of dibutyltin dilaurate was added, and the mixture was stirred at room temperature for 1 day. The disappearance of νNCO absorption was confirmed by IR spectrum, and the target resin was obtained with a polymerization rate of 78% and ▲ ▼ = 7700.

Example 5 t-Butyl hydroperoxide-blocked acyl isocyanate and a copolymer having a double bond as a pendant 3.1 g (28 mmol) of methacryloyl isocyanate, 4.7 g of n-butyl acrylate, 3.4 g of methyl methacrylate and 2 as an initiator 300 mg (3%) of 2,2'-azobis (2,4-dimethyl) valeronitrile (V-65) was mixed and added dropwise to 17.0 g of butyl acetate heated to 85% over 1 hour. Then, after aging for 1 hour, it was cooled to 10 ° C and 2.0 g (15.6 mmol) of 2-hydroxyethyl methacrylate was added to butyl acetate.
What was diluted to 1 g was added dropwise. Then 8.0 g (12.4 mmo) of 14% t-butyl hydroperoxide in dichloroethane
l) was diluted with 16 g of butyl acetate and added dropwise. The t-butyl hydroperoxide dichloroethane solution was used by extracting the t-butyl hydroperoxide aqueous solution several times with dichloroethane and then drying with Mg ₂ SO ₄ to determine the content by NMR. After completion of dropping, the mixture was stirred for 0.5 hours, the disappearance of absorption of νNCO was confirmed by IR spectrum, and the target resin was polymerized at a polymerization rate of 7%.
It was obtained at 5%, 75%, ▲ ▼ = 8800.

Example 6 Copolymer with t-Butyl Hydroperoxide and Phenol Blocked Acyl Isocyanate 3.1 g (28 mmol) methacryloyl isocyanate, 4.7 g n-butyl acrylate, 3.4 g methyl methacrylate and 2,2'-as initiator Azobis (2,4-dimethyl) valeronitrile (V-65) (300 mg, 3%) was mixed and added dropwise to 17.0 g of butyl acetate heated to 85 ° C over 1 hour. Then, after aging for 1 hour, it was cooled to 10 ° C and phenol 1.
What diluted 47 g (15.6 mmol) with 1 g of butyl acetate was added dropwise. Next, 8.0 g (12.4 mmol) of a dichloroethane solution containing 14% of t-butyl hydroperoxide was diluted with 16 g of butyl acetate and added dropwise. The t-butyl hydroperoxide dichloroethane solution was used by extracting the t-butyl hydroperoxide aqueous solution several times with dichloroethane and then drying with Mg ₂ SO ₄ to determine the content by NMR. 0.5 after dropping
After stirring for an hour, the disappearance of νNCO absorption was confirmed by IR spectrum, and the target resin was obtained at a polymerization rate of 70% ▲ ▼ = 8500.

Example 7 Hexane was added to each of the polymers obtained in Examples 1 to 4 and solid contents were taken out, and a sample washed several times with hexane was mixed with ethylene glycol dimethacrylate and n-butyl acrylate, Gelation due to initiation of radical polymerization was observed by heating to 120 ° C.

Example 8 Hexane was added to the copolymer obtained in Example 5, solids were taken out, and a sample washed several times with hexane was redissolved in butyl acetate. By heating this to 120 ° C, gelation due to initiation of radical polymerization was observed.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08F 216/00 MKU 218/00 MLE 220/06 MLU 7242-4J 220/58 MNG 226/02 MNL

Claims (4)

[Claims] 1. A formula: [In the formula, R ¹ is hydrogen or a lower alkyl group, and R is 2 carbon atoms.
An alkyl group or a ketoalkyl group which may have an aromatic ring and has A to A, A is a direct bond, Indicates. ] And the formula: [Wherein P, Q, Y and Z are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aralkyl group having 10 or less carbon atoms, a halogen, a cyano group, -O -COR '(R' is an alkyl group having 1 to 6 carbon atoms,
An aryl group having 8 or less carbon atoms, an alkylaryl group, a haloaryl group, an alkoxyaryl group, a haloalkyl group having 4 or less carbon atoms, or a hydroxyalkyl group is shown. ), Cyanomethyl group, amide group, —CH ₂ OCOR ″
(R ″ is an alkyl group having 9 or less carbon atoms, a haloalkyl group,
Or a phenyl group is shown. ) COORa (Ra is hydrogen, an alkyl or alkenyl group having 1 to 20 carbon atoms, an aryl group having 10 or less carbon atoms, an aralkyl group having 10 or less carbon atoms, a sulfoalkyl having 2 to 6 carbon atoms, or 2 to 3 carbon atoms) Of the formula (I), wherein the number of repeating units of the formula (I) is m (where m is a positive integer) and the repeating unit of the formula (II) is A polymer having n number (n is 0 or a positive integer) and having a molecular weight of 1,000 to 100,000. 2. The formula: [In the formula, R ¹ is hydrogen or a lower alkyl group, and R is 2 carbon atoms.
An alkyl group or a ketoalkyl group which may have an aromatic ring and has A to A, A is a direct bond, Indicates. ] The peroxide monomer represented by: [Wherein P, Q, Y and Z are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aralkyl group having 10 or less carbon atoms, a halogen, a cyano group, -O -COR '(R' is an alkyl group having 1 to 6 carbon atoms,
An aryl group having 8 or less carbon atoms, an alkylaryl group, a haloaryl group, an alkoxyaryl group, a haloalkyl group having 4 or less carbon atoms, or a hydroxyalkyl group is shown. ), Cyanomethyl group, amide group —CH ₂ OCOR ″ (R ″
Represents an alkyl group having 9 or less carbon atoms, a haloalkyl group, or a phenyl group. ), COORa (Ra is hydrogen, carbon number 1-2)
0 alkyl group or alkenyl group, aryl group having 10 or less carbon atoms or aralkyl group having 10 or less carbon atoms, 2 carbon atoms
Is a sulfoalkyl having 6 to 6 or an acid phosphoroxyalkyl having 2 to 3 carbon atoms. ] An ethylenically unsaturated monomer represented by the formula, characterized by polymerizing: [Wherein R ¹ , R and A have the same meanings as described above. ] And the formula: [Wherein P, Q, Y and Z have the same meanings as described above. ] A repeating unit represented by the formula: wherein the repeating unit of the formula (I) is m (where m is a positive integer) and the repeating unit of the formula (II) is n (where n is 0). Or a positive integer) and a method for producing a polymer having a molecular weight of 1,000 to 100,000. 3. The method according to claim 2, wherein the polymerization is carried out in a solvent inert to the polymerization. 4. A formula [Wherein R ¹ is hydrogen or a lower alkyl group, A is a direct bond, Or an isocyanate compound represented by the formula: [Wherein P ', Q', Y'and Z'independently represent hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an aralkyl group having 10 or less carbon atoms, halogen, cyano. Group, -O-COR '(R' represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 8 or less carbon atoms, an alkylaryl group, a haloaryl group, an alkoxyaryl group or a haloalkyl group having 4 or less carbon atoms). cyanomethyl, -CH ₂ OCOR "(R" is number 9 an alkyl group having a carbon
A haloalkyl group or a phenyl group is shown. ) Or CO
ORa (Ra is an alkyl group having 1 to 20 carbon atoms, an aryl group having 10 or less carbon atoms, or an aralkyl group having 10 or less carbon atoms). ] It polymerizes with the ethylenic unsaturated monomer which does not have the active hydrogen represented by these, Then, at least one part of an isocyanate group and Formula: HO-OR [In formula, R has a carbon number of 2-12, and an aromatic ring is represented. An alkyl group or a ketoalkyl group which may be included is shown. ] The formula characterized by reacting the hydroperoxide represented by: [Wherein R ¹ , R and A have the same meanings as described above. ] And the formula: [Wherein P ′, Q ′, Y ′ and Z ′ are as defined above. ] A repeating unit represented by the formula: wherein the repeating unit of the formula (I) is m (where m is a positive integer) and the repeating unit of the formula (II) is n (n is 0 or positive). An integer) existing and having a molecular weight of 1,000 to 100,000.